Treating recycle gas



Oct. 24, 1961 R. T. KELLEY ETAL TREATING RECYCLE GAS 3 Sheets-Sheet 1 Filed Dec. 1, 1958 momwmmmio O mowwmmaio wmommm T o E om mmmEo z s5 l I N i N m 2: mm m M3000 $3000 .50 mp2; zo s xoozx Fill.

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Inventors Attorney 3,005,8tl8 TREATHQG RECYCLE GAS Roland Timothy Kelley and James Edward Walker, Baton Rouge, La, and Bruce R. Tegge, Madison, NJ, assignors to Esso Research and Engineering Company,

a corporation of Delaware Filed Dec. 1, 1958, er. No. 777,269 Claims. (Cl. 260-853) This invention relates to an improved continuous proc/ ess for preparing a rubbery polymer and more particularly to a method for treating the recycle diluent from the butyl rubber polymerization process.

It is known in the preparation of butyl rubber that a stream is formed overhead in the flash drum by vaporization of the reactor etiiuent overflow slurry stream. The flash gases contain the diluent methyl chloride, hydrocarbon monomers, and water vapor. in the past, this stream has been compressed, dried, fractionated, and returned to the reactor as recycle monomer and diluent. However, it has been found the alumina driers which remove the water in this stream become saturated in a relatively short time, e.g., 24 hours. Therefore, the saturated alumina drier must be frequently replaced and regenerated; but these operations are expensive and time consuming.

Furthermore, it has been noted that polymerization poisons are formed during the preparation of the rubbery polymer. These poisons are hydrolysis products of methyl chloride and water, e.g., alcohols and ethers. It should be noted that most of these poisons are produced in zones in which water is present in large concentrations. These zones are the flash tank, the first stage recycle gas compression system, and the alumina driers. Moreover, alumina is an etfective catalytic agent for promoting hydrolysis. The primary hydroly-tic reactions of methyl chloride and methylene dichloride are summarized in the following reactions:

CH3Cl+CHsOH- CH3O CHa+HCl Subsequent reactions of these intermediate and final hydrolytic products with methyl chloride as inreaction (3) may form the following compounds: dimethyl ether; dimethoxymethane; methyl chloromethylether; bischloromethyl ether; and dichlorornethyl formal. Other types of oxygenated compounds would include tertiary butyl alcohol, and the products of the reaction of tertiary butyl alcohol and tertiary butyl chloride with methyl chloride, methylene dichloride, and the hydrolysis products of the latter two chlorides. Among these may be tertiary butyl methyl ether, ditertiary butyl formal, and tertiary butyl chloromethyl ether. These poisons described above have a deleterious effect upon the polymerization reaction by depressing the molecular Weight of the polymer and by reducing catalyst efficiency.

We have discovered a method whereby the life of an alumina drier can be extended to substantially longer periods of time, e.g., five days or more. Furthermore, it is now possible to remove a considerable amount of the nefarious molecular weight poisons from the recycle monomer and diluent stream. Thus, in accordance with one embodiment of this invention, the recycle stream from the flash tank is compressed and cooled; subsequently treated with a glycol solution; and then passed through alumina driers.

unreacted 3,065,898 Patented Oct. 24., i961 This invention may be fully understood from the following description with the accompanying drawings in which FIG. 1 shows the process previously employed, FIG. 2 demonstrates the improved process in accordance with the present invention, and FIG. 3 indicates another embodiment of this invention.

Referring now to FIG. 1, a vaporized stream comprising methyl chloride, water, unreacted hydrocarbon monomers, and polymerization poisons are withdrawn from the overhead in flash drum 1 and transported through water cooler 3 to knockout drum 5. In this drum 5, a small portion of the water in the stream is removed through line 6. From the knockout drum 5 is withdrawn a stream which comprises the same compounds with slightly less water therein and this stream is introduced by means of line 7 into the first stage of recycle gas compressor 10. After the stream is compressed, it is passed through water cooler 12 and through ammonia cooler 14 to knockout drum 15 where additional water is removed by means of line 16. The stream which still has a considerable amount of water therein, is transported to alumina driers 2t! where all the water in the stream is removed. A dry stream containing trace quantities of polymerization, poison as well as the unreaoted hydrocarbons and methyl chloride diluent, is withdrawn from outlet 21 and passed through the second stage of the re cycle gas compressor 22 and recycle distillation system 24 to provide a stream which is eventually recycled to the polymerization reactor by meansof line 25. I However, in accordance with this process, the alumina driers have to be regenerated daily, and furthermore the polymerization poisons which remain in the recycle stream have a deleterious effect upon the over-all process.

Referring now to FIG. 2, in accordance with this invention, a stream comprising water, methyl chloride, uh reacted hydrocarbons, and polymerization poisons from flask tank 1 is passed through water cooler 3, knockout drum 5, first stage recycle gas compressor 10, and water cooler 12 in a similar procedure to the one previously described in FIG. 1. However, the stream from cooler 12 in the present invention is passed directly into knockout drum 15; therefore, the ammonia cooler is eliminated in this process. Again, some of the Water is removed from the stream in the knockout drum 15 by means of line 16; however, a considerable amount of water remains therein. Therefore, in accordance with this invention, the stream from knockout drum 15 is transported through line 30 to a glycol absorption tower 32. A glycol solu tion is introduced at the top of tower 32 through line 34. The function of this tower 32 is to remove most of the water from the stream and thereby lessen the burden which is placed upon the alumina driers. Furthermore, the glycol solution removes a substantial quantity of the polymerization poisons from the system. From the bottom of tower 32 is withdrawn the glycol solution with water, polymerization poisons, and some methyl chloride which has been absorbed therein; and this solution is transported by means of line 36 to glycol regeneration system 38. In this regeneration system 38, glycol is recovered and returned to the absorption tower 32 by means of line '34. However, another function of the regeneration system 38 is to recover methyl chloride which is withdrawn and transported through line 40 as recycle for water cooler 3. From the top of tower 32 is withdrawn a stream of methyl chloride and unreacted hydrocarbons which contains considerably less water and less polymerization poisons therein. This overhead stream 42 is introduced into alumina driers 20 wherethe small amount of water remaining is removed from the stream. It is possible to eliminate the alumina driers entirely if the glycol system is efiicient enough. The dry stream is h iaseti h oi e o d ta evrmr s ri a tisecycled distillation system 24 to provide a stream which can be recycled by means of line 25 to the polymerization reactor. -Thus-,.it is now possibleto remove most of the water-which isproducedin the preparationzof .butylrub; ber before the, recycle stream comes in contact with alumina ,driers. Therefore, thedriers only requireregener-ation. about-once every 3 to 7 days. Furthermore, polymerization poisons are removed frorrrthe recycle-stream and the catalyst efliciencyis improved. I Also thedcpressing of the-molecular weight of the butyl rubber polymer has been alleviated in this invention. .;-The butyl rubber polymer of this invention is prepared by greacting 70 to 99 :v parts by weight, preferably 85 to 99.5, of an isoolefin with 30m 0.5 parts by weight, preferably to 0.5, of. multiolefin. The. isoolefin, .in general, is 1C ,to C- compound, e.g., isoobutylene ,or- 2- methyl-l-butene. The multiolefimmingeneral, is a C to Cm conjugated diolefin, e.g., isoprene, butadiene, or piperylene. v,The preferred polymeris obtained by reacting 9-5 to. 99.5 by weight of isobutylene'with 0.5 to 5% by weight; of isoprene. g V I Mixture of monomers, preferably with l to:5 volumes of'inertdiluent, e.g., methyl chloride, should be cooled to a temperature between 0 and. -200 ,C.,.and it is preferred that the temperature range be between: '-60 and .:130-" 1C. The cold mixture is polymerized by the addi- 0 l to 2 gallons of glycol solution are required per pound of water entering the absorption tower. W Although any alkylene or polyalkylene glycols may be application to this invention, it is preferred to use an ethylene glycol, di-, or triethylene. glycol. Other glycols that can be used include: propylene "glycol, polypropylene glycol, 'trimethylene' glycol, pentaglycol, butylene glycol, tetramethylene glycol, 1,3-bi1tandiol, methylpropandiol, pentandiol,- 3-methyl-1,3-butandiol, pinacol'," 2-methyl- 2,4-pentandiol. The solution generally has a concentration of glycol .within ya lrange of 95'to 99.8 wt. percent It is also within the purview of this invention to replace party of the glycol with an amine. Ihe preferred, amines are mono-, di and. tri lkanol amines, but the especially Preferred compounds are mono-,. di-, andj triethanol amines. A glycol-amine solution generally; comprises 10 to 3 0 wt. percent.of the amine and 65 to 89:..5% of the y t, a i f' 1 It should be noted that a glycol regeneration system can be provided for-recovering the'glycol from the efllu ent of the absorption tower. Furthermore, inthis regeneration system methyl chloridecan be recovered and r-ecycled to the first water cooler which is proyided after ,tionof a Friedel-Crafts catalyst, preferably an aluminum ha-lide'catalyst in a;.liquid or-dissolved-form, in conjunction ,with ivigorousagitation- The amount-of; catalyst is generally about 0.02 .to 0.5% by weight-of the mixed olefins. .1 w a I The polymerization reaction-1's rapidandthe polymer precipitates out of the solution in the form of a-slurry or fiocculent white-solid. The polymer, whichis-recovered in a flashtank .and'dried; has a staudinger rnolecular Weight.between-30,000 and 150,000, preferably 40,000 to 60,000;- andanziodinenumber 'between 0.5 and 50;.preferably betweenl sand 15. lThepreparation of this copolymer is =1described-in 1 U'.S.Patents 2,455,665; 2,356,128; and,,2,61-1,751 which; are included hereinby reference. Thebutyl rubber also within the scope of this invention the ,flash,tanlt., v. v. I

The overhead efiluent fromthe absorption tower co prises 0.0310 0.00 wt. percent water, to 9.0 wt. percentunreacted hydrocarbons, and 99 to 91 Wt. percent methyl chloride.- This overhead. effiuent isthen sent through the alumina drier, compressor, and fractionation system to provide-a recycle stream for the polymerization reactor.

The addition the glycol absorptionitoweritor process removes mostof the Water from the system prior includesdhosewhich are halogenated, etg dchlor'inated and :brominated; the preferredr'ange of halogen :in the mbbenstructure isfrom 0.9 to 1.5 wt. percent for ch10? rinatedbutyl rubber-and 1 .5 to 3.0' wt. percent fon'broiminatedrbutyl rubber. 3

.Fromthe overheaddn the flash drum is-provided 'a streamcomprising a rangeof 90.0 to 98.0%.methyl chloride,-.0 .4% .to- 1.0 Water," 1.0 to 9.0% :unreacted hydrocarbonsand traces of polymerization poisons. After this stream; is passed; through va series of. coolers,,-knockout I drums, and. compressors, it is'treatedywith aiglycol solutionin anabsorption' tower. Aboutj to;10 gallons. of glycol-solutionflareeprovided-for every; pound of water enteringihetower in the recycle :streamand about: (X94 poisons-are. absorbed therein.; In another embodirnent of this-invention "shown in FIG. ?3, the processvapors from knockout. drum ISIare further-:comp'ressed by second stage compressor-22 and then/fed toithe :bottom of glycol absorptiont'ower .32. g

7 methyl" chloride.

to drying with alumina; therefore, less frequent regem eration of the driers is required. Furthermore, the rernoval ofsome. of the poisons from therecycle. stream, inaccordance with this, invention, provides greater, uniformi-ty ofvcatalyst solvent and polymerization diluent and therebygives betterreactor-control and polyrner quality. ,In additiontheretopthe .ammonia coo lersican be eliminated in the present processrt'lherefore, this invention alleviates theserious disadvantages which were previously encountered in the process for preparing butyl rubber. i

I The following examples 'are submitted to illustrate and not to limit thisinvention. f

, Examplel i A feed of isobutylene and isoprene was introduced into "a'reactor and polymerized in the presence of an aluminum chloride catalyst'and me ayr chrome as a diluentto provide a butyl polymer o f-LS Incl per ent nsamiatien; The'jpoiym'er slurry formed therein was introduced into afiash tank whereinja' 'yapor 'stre'arn st awberrie ever: head comprising wt percenlt methylchloride', lj iwt percent 'water, 3;5' 'wt.- percent unrea'ct'e'd hydrocarbons, and trace amounts of polymerization poisons. ,This stream 'Was' thenpa'ssedthrough 'a-serie's' 'f coolers, knockout drums, and compressors and introduced into 'a glycol absorption tower. The stream entering this towei container 0.54 wt. percent water based onfm'ethyl chlo ride. 'A'98'wt; percent'aqueous tliethylene glycollsolution was introduced into the tower at farmer '5, gallons TEG/l ibqn o. The recyclestre'am'ivas comatose/uh the glycol solution and subsequently withdrawn frdiiitue tower," The amount 'ofwa'te'r remaining in the' 'effiuent stream was determined to be 0.18 wtfpercent b'a's pressure .v'a uejp el- The amount ofwatefr Another run yvas performed in which" the" the tower'was increased'from the 42.7 p.s'.i viously'used,'i'to';113i2 p.s.-i.a.' I entering the tower'was again I 0.5 wt. percent. Hdweve'r; the amount of water remaining in'the streamj aft'er it was contacted with the 'triethylene glycol 5 solution" was determined to be 0.013 wt. percent ru thmierejifi both runs, it was noted that the amount of polymerization poisons in the overhead stream from the tower, was substantially decreased.

Accordingly, therefore, this example demonstrates that incorporating a glycol absorption tower and contacting the recycle stream with a glycol solution before it is passed through the alumina driers has a beneficial effect upon the butyl rubber polymerization system. In accordance with this invention, considerably less water enters the alumina driers and therefore less expense will be involved in regeneration. Furthermore, removing some of the polymerization poisons in the system provides greater catalyst activity and uniformity and improved polymer quality.

Example 11 In this example the flashed gases from the water slurry tank were passed through a series of coolers, knockout drums, first and second stage recycle gas compressors and introduced on the 27th tray of a 30-plate glycol dehydrating tower. The stream from the second stage recycle gas compressor entered the tower at a temperature of 270 F. and a pressure of 200 p.s.i.a. The stream consisted of 6804 lbs./ hr. of methyl chloride, 710 lbs/hr. of unreacted hydrocarbons, and 44 lbs/hr. of water. 99.8 wt. percent ethylene glycol solution was introduced to the 5th plate of the tower at a rate of 400 lbs/hr. The recycle stream was thus contacted with the glycol solution and subsequently withdrawn from the top of the tower at conditions of 140 F. and 190 p.s.i.a. The overhead vapor of 9575 lbs./ hr. was condensed and 2200 lbs/hr. was returned to the top of the tower as reflux. The remaining 7250 lbs/hr. of dry recycle methyl chloride and isobutylene contained 12 p.p.m. of water and was sent to the recycle fractionation system. The bottom stream from the glycol dehydrating tower contained 44 lbs/hr. of water, 400 lbs/hr. of ethylene glyco, 204 lbs/hr. methyl chloride, and 60 lbs/hr. of C and C hydrocarbons. This stream was fed to the top of a glycol regeneration tower in order to remove the water, methyl chloride, and C and C hydrocarbons from the glycol solvent. The glycol regeneration tower contained 15 plates and was operated at a pressure of 1.5 p.s.i.a. with top and bottom temperatures of 120 F. and 300 F., respectively. The overhead stream from this tower containing 204 lbs/hr. of methyl chloride, 44 lbs/hr. of water, and 60 lbs./ hr. of C and C hydrocarbons was returned to the water flash tank of the recycle gas system. The bottoms from the glycol regeneration tower contained 400 lbs/hr. of glycol and 0.8 lb./l1r. of water. This stream was cooled from 300" F. to 140 F. before it was recycled to the 5th plate of the glycol dehydrating tower.

It will be noted that the water in the overhead recycle stream from the glycol dehydrating tower amounted to only 12 ppm. As a result it was not necessary to pass this stream through the alumina dryers for further water removal and the alumina dryers were by-passed.

Having described the general nature and specific embodirnents of the present invention, the true scope is particularly pointed out in the appended claims.

What is claimed is:

1. An improved continuous process for preparing butyl rubber which comprises polymerizing a mixture of a major amount of C to C isoolefin and a minor amount of C to C conjugated diolefin, said polymerization being carried out in the presence of a Friedel-Crafts catalyst at temperatures between about -l30 C. and -60 C. in a methyl chloride diluent so as to form a slurry of the polymerized product in said diluent together with unreacted monomers and oxygen-containing organic polymerization poisons, admixing said slurry with water of sufiiciently high temperature to produce a vaporized first stream comprising water, diluent, unreacted monomers and oxygen-containing organic polymerization poisons,

transporting said first stream through a series of cooling, knockout and compressing zones so as to remove gross amounts of water content therefrom, intimately contacting the resultant first stream in an absorption zone with a solution of an alkylene glycol having from 2 to 6 carbon atoms, withdrawing from said absorption zone a second rafiinate stream containing less water and polymerization poisons than said first stream, drying said second stream in the presence of alumina, and fractionating said dry stream to form a recycle stream for the polymerization reaction.

2. The process according to claim 1 in which the glycol solution comprises to 99.8 wt. percent of a glycol selected from the group consisting of diethylene glycol, triethylene glycol, and ethylene glycol.

3. The process according to claim 1 in which the glycol solution comprises 95 to 99.8 Wt. percent of diethylene glycol.

4. The process according to claim '1 in which the glycol solution comprises 95 to 99.8 wt. percent of triethylene glycol.

5 The process according to claim 1 in which the glycol solution comprises 95 to 99.8 wt. percent of ethylene glycol.

6. The process according to claim 1 in which the glycol solution comprises 65 to 89.8 wt. percent of an alkylene glycol and 10 to 30 wt. percent of an alkanolamine.

7. The process according to claim 1 in which the glycol solution comprises 65 to 89.8 wt. percent of triethylene glycol and 10 to 30 wt. percent triethanolamine.

8. An improved continuous process for preparing butyl rubber which comprises polymerizing a mixture of a major amount of C to C isoolefin and a minor amount of C to C conjugated diolefin, said polymerization being carried out in the presence of a Friedel-Crafts catalyst at temperatures between about l30 C. and 60 C. in a methyl chloride diluent, thereby forming a slurry of the polymerized product in said diluent together with unreacted monomers and oxygen-containing organic polymerization poisons, admixing said slurry with water of sufiiciently high temperature to produce a vaporized first stream comprising water, methyl chloride diluent, unreacted monomers and oxygen-containing organic polymerization poisons, transporting said first stream through a series of cooling zones, knock-out zones, first and second stage compressing zones so as to remove gross amounts of the water-content therefrom, passing the resultant first stream into an extraction and solvent distillation zone wherein said stream is intimately contacted with a solution of an alkylene glycol having from 2 to 6 carbon atoms, withdrawing from the top of said absorption and solvent distillation zone a dry second raffinate stream, condensing said dry second stream, refluxing part of said condensed second stream to said absorption and solvent distillation zone, fractionating the remaining part of said condensed second steam to provide a recycle stream for the polymerization zone, withdrawing from the bottom of said absorption and solvent distillation zone a third stream containing water, methyl chloride, unreacted monomers and alkylene glycol, transporting said third stream to a regeneration zone to provide substantially pure alkylene glycol for recycle to said absorption and solvent distillation zone.

9. In the continuous process of producing butyl rubher from the polymerization of a mixture of a major amount of C to C isoolefin and a minor amount of C to C conjugated diolefin, said polymerization being carried out in the presence of a Friedel-Crafts catalyst at a temperature of between about C. and 60 C. in a methyl chloride diluent so as to form a slurry of the polymerized product in said diluent, and thereafter intimately mixing said slurry with water of a temperature sufficiently high to produce a vaporized stream comprising water, methyl chloride diluent, unreacted monomers and oxygen-containing organic polymeriza-v tion poisons, and transporting isaid stream through ;;a seriesmf cooling;- knockout and compressing-zones :so asto remove grossr amounts of watercontent ,there-from, the: improvementwhich comprises intimately contacting said vaporized :resultant stream with ;a solution of an alkyleneiglyicol having from 2 tot61carho11 atoms to substantially reduce; the l arnou nt of water and oxygen-con: taining organic-polymerization'poisons contained there-r inbefore utilizing the resultant vaporized rafiinate stream as recycle material in the polymerization process.-

J 10. The. process according/etc. claim ,wherein the glycol solutioneo mprises 95 to 99;8.;Wt..-tpercent;of a glycol; selected :from th'eqelass consisting ofxliethylene glycol, triethylene glycol and ethylene-glyi ol.

::: References filter in theme of this patent; 1;

2,636,025 I-Iowe et al. V 725 58 7 8 Belem t P i ITHERJRE EREMESL K Handboo STATES' PA n gp Chem. l'vol: 3 8' 1946 pages dlEngQbhem l v51. 40' K1948);

Ofc misnyJ; 1946; pages 5:10. 

1. AN IMPROVED CONTINUOUS PROCESS FOR PREPARING BUTYL RUBBER WHICH COMPRISES POLYMERIZING A MIXTURE OF A MAJOR AMOUNT OF C4 TO C7 ISOOLEFIN AND A MINOR AMOUNT C4 TO C10 CONJUGATED DIOLEFIN, AND POLYMERIZATION BEING CARRIED OUT IN THE PRESENCE OF A FRIEDEL-CRAFTS CATALYST AT TEMPERATURES BETWEEN ABOUT -130*C. AND -60*C. IN A METHYL CHLORIDE DILUENT SO AS TO FORM A SLURRY OF THE POLYMERIZED PRODUCT IN SAID DILUENT TOGETHER WITH UNREACTED MONOMERS AND OXYGEN-CONTAINING ORGANIC POLYMERIZATION POISONS, ADMIXING SAID SLURRY WITH WATER OF SUFFICIENTLY HIGH TEMPERATURE TO PRODUCE AS VAPORIZED FIRST STREAM COMPRISING WATER, DILUENT, UNREACTED MONOMERS AND OXYGEN-CONTAINING ORGANIC POLYMERIZATION POISONS, TRANSPORTING SAID FIRST STREAM THROUGH A SERIES OF COOLING, KNOCKOUT AND COMPRESSING ZONES SO AS TO REMOVE GROSS AMOUNT OF WATER CONTENT THEREFROM, INTIMATELY CONTACTING THE RESULTANT FIRST STREAM IN AN ABSORPTION ZONE WITH A SOLUTION OF AN ALKYLENE GLYCOL HAVING FROM 2 TO 6 CARBON ATOMS, WITHDRAWING FROM SAID ABSORPTION ZONE A SECOND RAFFINATE STREAM CONTAINING LESS WATER AND POLYMERIZATION POISONS THAN SAID FIRST STREAM, DRYING SAID SECOND STREAM IN THE PRESENCE OF ALUMINA, AND FRACTIONATING SAID DRY STREAM TO FORM A RECYCLE STREAM FROM THE POLYMERIZATION REACTION. 